Azo dyestuffs insoluble in water, and fiber dyed therewith



Patented Feb. 17, 1942 v UNiT-Eo STATES PATENT OFFICE A'ZO DYEST'UFFS 'INSOLUBLE IN WATER, AND FIBER :DYED THEREWITH Georg Kritnz'lein and Carl Josef Miillcr, Frank- Ifort-on-Tthe-Main Hochst, Germany, assignors to General Aniline & Film Corporation, New York, N. Y., a corporation of-Delaware No Drawing. Application September 4, 1940, Serial No. 355,306. -In Germany November 9, 1938 12-Claims. (Cl. 260-192) The present invention relates to 'azo-dyestufis by volume are related to each other as are kiloinsoluble in water and to fiber dyed therewith; grams to liters: more particularly it relates to dyestuffs correspendin with th u m general iormula; 1. Groundmy solution X 5 -6 parts of 1-(2'.3'-hydroxynaphthoylamino)- I benzene are dissolved, while heating, in N 6 parts by volume of alcohol,

1 3 parts by volume of formaldehyde solution Q of 30 per cent strength and 10 3 parts by volume of caustic soda solution on Q of 34 B. and the solution is introduced into a solution of CONH-R parts by volume of Turkey red 'oil and parts by volume of caustic soda solution of wherein R'means a radical of the benzene or f B in I I naphthalene series and X stands for a substituent, 1900 parts Volume Watersuch as halogen, an alkyl, alkoxy or trifluoroy -group. Developing SO UtZOn We have found that valuable azo-dyestufis, in- 0 2.055 parts of the acid, diazonium sulfate 0bsoluble in water, may be obtained by coupling in tainable by diazotization of 1.51 parts of 1- substance, .on the fiber or on a substratum amino-3-bromanthraquinone, are dissolved at adapted for the production of lakes a di-azoroom temperature in 1000 parts by volume of compoundof a laminoanthraquinonecontaining water with addition of 1 part of acetic acid of in 3-posi-tion a substituent, such as, for instance, 50 per cent. strength.

halogen, an alkyl-, alkoxyor trifluoromethylgroup, with an arylide of 2.3-hydroxynaphthoic Dyemg 9 acid, neither of the components containing any 50 parts of cotton yarn or mixed fabric fmm group F j t 3 as, instance cotton and viscose staple fiber are treated in the sulfomc acid or carboxyhc acid groups.

In this manner vivid scarlet and red shades of good properties of fastness are obtained. In comparison with the known azo-dyestufis from unsubstituted l-diazo-anthraquinone the new dyestuffs represent a considerable technical advance; they have generally a better fastness to light and to soaping and throughout an essentially clearer shade. A special advantage of the invention 'resides in the fact that the diazo-compounds used f corresponds wlth the fonowmg are rather soluble in water. This behavior of the 40 Orm substituted l-diazo-anthraquinones could not be B r foreseen, since it is known that amino-compounds 1 carrying substituents, especially those of negative N N character, in general yield diazonium compounds The material is then well squeezed and introduced into the developing solution. After half an hour the coupling is finished. The material is well rinsed, 'soaped at boiling temperature, rinsed again and dried.

A bright scarlet of very good fastness to light is obtained.

which are more sparingly soluble in water than those of the unsubstituted amino-compounds.

The following examples serve to illustrate the OH 6 invention, but they are not intended to limit it I thereto, the parts being by weight unless 'other- \OONH wise stated; the parts by weight and the parts grounding solution at 20 C. for half an hour- 2. 15 parts of 1-(2'.3-hydroxynaphthoylamino)- benzene, 15 parts by volume of Monopol brilliant oil and 20 parts by volume of caustic soda solution of 38 B.

are dissolved in boiling water and the whole is made up to 1000 parts by volume. Fabrics from cotton or viscose staple fiber are padded with this solution. The material is then dried and printed with a printing paste which has been obtained by dissolving 26 parts of the acid diazonium sulfate from 1-amino-3-bromanthraquinone in parts of acetic acid of 50 per cent strength 515 parts of water and 450 parts of starch tragacanth thickening.

means of l-diazo-anthaquinone, are very uniform also when produced with a printing paste reduced 1:5 or 1:8.

3. Fabric made from cotton is grounded on the foulard as described in Example 2 with 1-(2'.3'- hydroxynaphthoylamino) -benzene, dried and then developed on the foulard with a. solution containing per 1000 parts by volume of water 30 The material dyed on the foulard is dried and printed with the following white discharge:

grams of sodium formaldehyde sulfoxylate grams of potash grams of sodium benzylsulfanilate grams of water grams of starch tragacanth thickening grams of titanium dioxide 1:1

grams of zinc white 1:1

grams of anthraquinone paste of 30 per cent strength 1 kilo.

The printed material is steamed for 5 minutes in a rapid ager and after-treated at boiling temperature with a solution containing per liter of water 1 gram of sodium carbonate and 1 gram of the product obtained by the action of ethylene oxide on isooctylphenol.

A pure white is obtained on a scarlet-red ground.

4. 27 parts of 1-(2'.3'-hydroxynaphthoylamino) -benzene are dissolved in hot dilute caustic soda solution, cooled to room temperature and 10 grams of calcined sodium carbonate are added thereto. A solution of 36.6 parts of the acid diazonium sulfate from 1-amino-3-chloroanthraquinone in water is then caused to run in. As soon as diazonium compound can no longer be detected, the solid matter is filtered with suction, washed and dried. A scarlet-red powder is obtained which dissolves in concentrated sulfuric acid to a dark red solution. The coupling may also be conducted in an acid, for instance acetic acid medium. The dyestuff may also be prepared in the presence of a substratum. It has a very good fastness to light, to oils and to overstriping.

The following table indicates a number of other azo-dyestuffs and tints obtainable by this invention:

Diazonium compound from Coupled with- Tint 1-(2'.3-hydroxynaphthoylamino)- 1 l-amino-ii-bromanthraquinone 4-chlorobenzene Scarlet-rod. 2 do 4-methoxybenzene Do. 3 2 methyb-i-chlorobenzene Scarlet.

2-(2'.3-hydroxynaphthoylam1 Naphthalene Scarlet-red. l- (2' .3-hydroxynaphthoylamino) l-5 2-methoxybenzene Do.

Naphthalene Yellowish red. x 2-methyl-4-chlorobenze Scarlet. 4-methoxybenzene. Red. 4-chlorobenzene D0. 2-methylbenzene Do. Benzene Scarlet. 2-methoxybenzene Do. 2-methyl-4-chlorobenzene Do. 2-methoxybenzene Do. 4-methoxybenzene Do. Z-methyM-chlorobenzene Yellowisb red 2-methylbenzene Scarlet. Benzene Yellowish red. 2-(2 .3 -hydroxynaphthoylamino) 19 -amino-3-meth0xyanthraquinone Naphthalene Do.

1- (2 .3 -hydroxynaphthoylamino) 20 1-amino-3-methylanthraquinone Benzene Red. 21 .do Z-methoxybenzene Do. 2 2-methylbenzene. Do. 2 4-chlorobenzene Do.

2-(2'.3'-hydroxynaphthoylam1no)- 24 Naphthalene Do.

parts of the acid diazonium sulfate from 1- amino-3--chloroanthraquinone. The material is then passed through the air for /2 to minute, then rinsed and soaped at boiling temperature; a very clear scarlet red tint of very good properties of fastness is obtained.

Since an object of the present invention is to provide dyestuffs of good fastness properties which dyestuffs are insoluble in water and alkalies, it is to be understood that the aromatic nuclei of the general formulae appearing in the appended claims do not contain any substituents wherein R means a member of the group consisting of radicals of the benzene and naphthalene series and X stands for a member of the group consisting of chlorine, bromine, methoxy, methyl and trifiuoromethyl,

being scarlet to red powders which have a very good fastness to light, to oils and to overstriping, and yielding, when produced on the fiber, vivid scarlet and red shades of good properties of fastness, especially of very good fastness to light.

2. The water-insoluble azo-dyestuffs corresponding with the following general formula:

wherein R means a radical of the benzene series and X stands for a member of the group consisting of chlorine, bromine, methoxy, methyl and trifluoromethyl,

being scarlet to red powders which have a very good fastness to light, to oils and to overstriping, and yielding, when produced on the fiber, vivid scarlet and red shades of good properties of fastness, especially of very good fastness to light.

3. The water-insoluble azo-dyestufis corresponding with the following general formula:

wherein R means a radical of the benzene series,

being scarlet to red powders which have a very good fastness to light, to oils and to overstriping, and yielding, when produced on the fiber, vivid scarlet and red shades of good properties of fastness, especially of very good fastness to light.

4. The water-insoluble azo-dyestufi of the following formula:

QIEiNH being a scarlet-red powder which has a very good fastness to light, to oils and to overstriping, and yielding, when produced on the fiber, very clear scarlet-red shades of good properties of fastness, especially of very good fastness to light.

5. The water-insoluble azo-dyestufi of the following formula:

I N D (11H: being a scarlet-red powder which has a very good fastness to light, to oils and to overstriping, and yielding, when produced on the fiber, very" clear scarlet shades of good properties of fastness, especially of very good fastness to light.

7. Fiber dyed with the water-insoluble dyestufis as claimed in claim 1.

8. Fiber dyed with the water-insoluble dyestuffs as claimed in claim 2.

9. Fiber dyed with the water-insoluble dyestufis as claimed in claim 3.

10. Fiber dyed with the water-insoluble dyestufi as claimed in claim 4.

11. Fiber dyed with the water-insoluble azodyestufi as claimed in claim 5. v

12. Fiber dyed with the water-insoluble dyestufi as claimed in claim 6.

GEORG KRKNZLEIN.

azo

azo- 

